DERIVATIVES  OF  O-TOLYL  ARSINE 


BY 


JOHN  STANTON  PIERCE 
B.  S.,  Georgetown  College,  1920 

THESIS 

Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 

Degree  of 

MASTER  OF  SCIENCE 
IN  CHEMISTRY 

IN 

THE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 


1921 


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UNIVERSITY  OF  ILLINOIS 

THE  GRADUATE  SCHOOL 

July  -EB 1 92X 

I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 

jr'  SUPERVISION  BY John  Stanton  Pierce  

ENTITLED  „ __  _ _I)aiLiy.at.ive_s_,.Ql  n-Xo.Iylarsine 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF Laster  oX.^nleuGO 


Recommendation  concurred  in* 


Committee 

on 

Final  Examination* 


^Required  for  doctor’s  degree  but  not  for  master’s 


476972 


Digitized  by  the  Internet  Archive 

in  2016 


https://archive.org/details/derivativesofotoOOpier 


TABLE  OF  GOIITELTS 


I. 

II. 

III. 

IV. 


V. 

VI. 


page 

Ac  knowl e d geme  nt 

Historical 2 

Theoretical 3 

Experimental 5 

Preparation  of  o-tolylarsinic  acid 
Preparation  and  properties  of  o-tolylarsine 
Condensation  of  o-tolylarsine  with  benzal- 
dehyde;  properties  of  condensation  product 
Condensation  of  o-tolylarsine  with  paraldehyde; 
properties  of  condensation  product. 


Suinmary 10 

Bibliography 11 


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Derivatives  of  o-Tolylarsine . 

I. 

Historical 

For  almost  a century  the  study  of  organic  arsenical  compounds 

has  been  of  great  interest  to  chemists,  fhis  interest  v/as  heisht- 

1 

ened  by  the  introduction  of  atoxyl  into  therapeutics  about  1902. 

The  synthesis  of  salvarsan  by  Ehrlich  in  1909  stimulated  to  a high- 
er degree  the  search  for  organic  arsenical  compounds  of  therapeutic 
value.  In  this  quest  of  new  arsenical  compounds,  the  preparation 
aJid  reactions  of  organic  arsines  have  been  studied  extensively. 


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II. 

Theoretical 

Phen;ylarsine , the  first  primary  aromatic  arsine  to  he  isolated, 
v/as  prepared  in  1901  hy  Palmer  and  Dehn.  Previous  attempts  to  is- 
olate primary  arsines  had  proven  unsuccessful  due  to  their  great 
ease  of  oxidation.  The  method  employed  hy  Palmer  and  Dehn,  the  re- 
duction of  an  arsinic  acid  with  amalgamated  zinc  dust  and  hydro- 
chloric acid  in  an  inert  atmosphere,  is  of  almost  universal  appli- 
cation for  the  preparation  of  primary  arsines. 

Oxidizing  agents  on  primary  arsines  give  a variety  of  products, 
the  relative  amounts  of  each  depending  mainly  on  the  strength  of 

the  oxidizing  agent,  although  other  factors,  such  as  solvent  and 

o 

concentration,  have  some  effect.  Strong  oxidizing  agents,  as  po- 
tassium permanganate,  take  the  arsines  all  the  way  to  the  correspon- 

4 

ding  arsinic  acids.  Milder  oxidizing  agents,  as  ferric  chloride, 

5 

oxidize  these  arsines  to  the  corresponding  arsinious  oxide.  With 

atmospheric  oxygen,  phenyl  arsine  gives  a m.ixture  of  phenyl-arsinic 

6 

acid,  phenyl  arsenious  oxide  and  arseno  benzene.  As  the  arsines 

are  so  easily  oxidized,  all  v/ork  ^vith  them  must  be  done  in  an  inert 

atmosphere.  Halogens,  with  the  primary  arsines,  also  give  a great 

variety  of  products,  among  which  are  arsenious  halides,  the  corres- 

7 

ponding  arsinic  acid  and  arsenious  oxide. 

The  primary  aromatic  arsines  form  a num.ber  of  condensation  pro- 
ducts with  a variety  of  different  reagents.  Thus,  they  react  with 

Q 

aryl  arsenious  chlorides,  and  aryl  stibinous  chlorides,  arseno  and 
arseno  stibino  compounds  respectively  being  formed.  Similarly,  v/ith 

arsenious  oxides,  arseno  compounds  are  formed.^  Some  substituted 

primary  aromatic  arsines,  with  salts  of  silver,  copper,  gold  and 

10 

platinum  form  addition  products.  With  the  chlorides  of  arsenic. 


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11 

above,  but  by  the  elimination  of  hydrochloric  acid. 

12 

With  alkyl  iodides,  quartenary  arsonium  compounds  are  form.ed. 

13 

Recently,  it  v/as  found  that  primary  arsines  condense  with  aldehyde. 
As  part  of  a series  of  experiments  to  see  whether  or  not  this  reac- 
tion is  general,  condensation  products  were  m.ade  of  o-tolylarsine 
with  benzaldehyde  and  paraldehyde. 


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Experimental 
o-Tolylarsinic  acid. 

14 

This  acid  was  prepared  hy  Bart's  method.  321  g.  of  o-tolui- 
dine  was  dissolved  in  a mixture  of  3 liters  of  v/ater  and  740  g.  of 
concentrated  hydrochloric  acid.  After  cooling  to  5°  a solution  of 
207  g.  of  sodium  nitrite  was  added  slov/ly  and  the  excess  acid  neu- 
tralized with  sodium  carbonate.  This  mixture  v;as  then  run  slowly 
into  a sodium  arsenite  solution  made  by  dissolving  716  g.  of  sodium 
carbonate  and  445  g.  of  arsenic  trioxide  in  3 liters  of  v/ater.  A- 
bout  50  g.  of  copper  sulphate  was  used  as  a catalyst.  During  the 
addition,  and  for  about  three  hours  after,  the  mixture  was  vigor- 
ously stirred.  Then  it  wa.s  filtered  from  tar,  acidified,  and  the 
o-tolylarsinic  acid  separated  from  the  solution  by  filtration.  The 
yield  was  260  grams,  v/hich  is  57%  of  theoretical.  Its  m:elting  point 
was  159!  An  attempt  was  made  to  increase  the  yield  by  evaporation 
of  the  m.other  liquor  but  so  much  sodium  chloride  and  so  little  o- 
tolylarsinic  acid  that  the  extraction  of  the  acid  would  not  have 
been  worth  the  tim.e  and  reagents  required. 

o-Tolyl  Arsine. 

In  the  reduction  of  o-tolylarsinic  acid  to  the  corresponding 
arsine,  runs  of  75  grams  of  acid  were  made.  This  v;as  v;ell  mixed 
with  300  grams  of  amalgamated  zinc  dust.  The  reduction  was  carried 
out  in  a 2 liter,  round  bottom  flashy  containing  the  above  mixture, 
and  about  500  cc  of  ether.  It  v/as  fitted  with  a dropping  funnel  and 
upright  condenser  with  mercury  seal  to  permit  hydrogen  to  escape  yet 
to  prevent  the  entrance  of  atmospheric  oxygen.  Concentrated  hydro- 
chloric acid  was  introduced  at  the  rate  of  seven  or  eight  drops  a 


6. 

minute  till  practically  all  of  the  zinc  had  reacted.  Then  the  ether 
v/hich  was  lost  hy  evaporation  v;as  replaced  and  the  ether  layer  si- 
phoned off  into  a flask,  and  dried  with  calcium  chloride.  The  ether 
solution  of  the  reduction  product  v/as  then  sucked  up  into  a Claisen, 
through  which  carhon  dioxide  v;as  passed  slowly,  and  the  ether  dis- 
tilled off.  The  linuid  left,  boiled,  with  slight  decomposition  at 
12 1'^  93mm  and  133”  131mm. 

It  v/as  found  more  convenient,  part  of  the  time,  to  distill  the 
reduction  product  without  drying  it  v/ith  calcium  chloride.  In  these 
cases,  the  distillate,  on  standing,  separated  into  tv;o  well  defined 
layers,  the  layer  of  water  on  top  serving  as  a protection  against 
atmospheric  oxygen,  which  sometime  leaked  into  the  apparatus. 

An  attempt  was  m.ade  to  distill  some  of  the  reduction  product 
at  atmospheric  pressure,  742  mm.,  but  it  practically  all  decomposed, 
giving  off  a fairly  heavy  cloud  of  smoke.  The  boiling  point  is  a- 
bove  152'’,  for  at  this  tem.perature , som.e  of  it  condensed  on  the  bulb 
of  the  thermometer. 

V/hen  the  hydrochloric  acid  was  added  at  the  rate  indicated  a- 
bove,  yields  of  about  32  grams  or  52f^  of  theoretical  were  obtained, 
r/hen  the  acid  v/as  added  faster,  likely  hydrogen  was  evolved  faster 
than  it  could  be  used  in  the  nascent  state  to  reduce  the  o-tolylar- 
sinic  acid.  In  the  longer  runs,  likely  the  arsine  formed  ?;as  oxi- 
dized to  a certain  extent  by  atmospheric  oxygen  leaking  into  the  ap- 
paratus . 

The  reduction  product  analyzed  for  o-tolylarsine  by  Robertson's 

15 

method  for  the  estimation  of  arsenic  in  organic  compounds. 


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iPlirn  . **  . .-■  *//'(! if 'ri  . •«  btt  ' vllvfim/:^  'd A', ■ CaJiMiW' ■*4’ ft’*") vaX,' 


*-V'6'r  viftj»«jwi!S»  , 


« ' <* 


MS  ' •■/^  ?i!4  ■ .-'  ^i*i' ',.i  \v^»a 

. W' . V ':■« ?^^>> '■  1 f. £.SJ4> r,  - ^ 


» ' ■”  • ■ 
‘J »'  ■•« 


i 


'4<<' 


-J  . 


S.,'!'".-  ' i)J/V  . ,;^  ■ w. 

K-  >!  / ■■•.  ' - J ' ’ .'J!  ' V*##®  ' ® 


';'i^fc;av“-v  • 'nf'  let  •a»'t*if^!i  'vr  '.:'‘'.i 

^'.1'  •!  W!-y,it,  i ,r>r..;^;i\4*-— i*»tVs^'  M® 


7 


Calculated  for  GH5C6H4ASH2  % arsenic 

44.60 

,2716  gram  substance  reduced  65.60  ac.of  io- 
dine solution  (lc.c.=  ,001792.  g.  arsenic)  43.28 

.3182  gram  substance  reduced  77,67  c.c,  of  io- 
dine solution  43.74 

,2526  gram  substance  reduced  61.69  c.c.  of  io- 
dine solution  43.76 

o-l'olylaraine , colorless  liq_uid  with  garlic  like  odor,  v/as  ra- 
pidly oxidised  by  atmospheric  oxygen.  Y/hite,  yellov/,  and  red  sub- 
stances were  present  in  the  oxidation  product.  The  v/hite  product 
was  o-tolylarsinic  acid,  as  was  shov.ii  by  its  melting  point,  fhe  yel- 
low compound,  v/hich  melted  at  205  - 208" probably  was  o-arsenotoluerfi. 
The  sample  for  analysis  was  recrystallized  from  benzene. 

arsenic 

Calculated  for  GHgCgH4As=  AsCgH/GHrz;  45.14 

.1530  gram  of  substance  reduced  20.18  c.c. 
of  iodine  solution  (1  c.c. -003515  g. 

arseiiic  ) 4^,36  I 

o-Tolylarsine  and  Benzaldehyde . 

To  15  grams  of  o-tolylarsine  kept  in  an  atm.o sphere  of  carbon 
dioxide  v/ere  added  about  eight  drops  of  concentrated  hydrochloric 
acid  and  18  gram.s  of  benzaldehyde , in  small  portions.  The  reduction 
mixture  soon  became  quite  v/arm  and  after  a short  period  of  time, 
partially  solidified.  Although  condensation  took  place  in  a few  minr 
utes,  apparently  the  reaction  vvas  more  complete  when  the  mixture 
was  allowed  to  stand  a few  days  in  an  inert  atmosphere.  After  sev- 
eral days  the  excess  benaaldohyde  was  filtered  off  with  suction,  and 
the  solid  left  on  the  filter  paper  extracted  v/ith  ether.  White, 
needle-like  crystals,  which  melted  at  140"were  obtained.  The  sample 
for  analysis  was  recrystallized  from  ether. 


^;V  ' 


^ , jj\,„ .' ' ' M%Mia0-  ^ 

»v'  ' ■ ?„m'  ' V ' 

r:  .J."  ; ^.  t>.  V /-'.lo 

f'  - .:,rvV/,M-3T/  r , ■.,  ,.^,  . v.,,  , .r-..,,,  ••  ^ u 

:w..'  '■■•3'.;i>  If  \'j 

S , ;■  .■■  • ' : ■ . /:.,^W  /' '|l;i  i 

ft  , s a h ^ ? I ■ » V . {:  i • v>  ^ ,#i.i  u "» a ' <>■  ! ■!  y 

^ ■'  ■ ■ ■■  .V 

' ••I  >V  J'  . * X ■ i . i'  1 -•  ' 1,‘P’  .1  V-iSf 


v,'^'  'ij’'5  W'  - ‘ 'i'  ' .*>’•■.  , . ' - iP'',r  ''>V4Jl’ ic-* 

1.^  ......  a- — ..^1^ ’^gpJajigajr.^^  ***  |..^1 .« 


8 


> arsenic 

Calculated  for  CH'^CgHaAsHoI  C5H5CHO )s  19.71 

.1507  gram  of  sulstance  reduced  8.03  c.c.  of 

iodine  solution  (1  c.c. **.003515  g.  arsenic)  18.73 

.1391  gram  of  substance  reduced  7.45  c.c.  of  io- 
dine solution  18.82 

T’he  above  product  evidently  was  a condensation  of  one  mole 

of  o-tolylarsine  and  two  moles  of  benzaldehyde . fhe  following  for- 


mula : 


is  a possible  and  probable  one.  This  condensation  product  is  hydro- 
lyzed by  cold,  concentrated,  hydrochloric  acid  and  slightly  by  boil- 
ing dilute  hydrochloric.  It  is  not  hydrolyzed  by  boiling  five  mxin- 
utes  with  30%  sodium  hydroxide  solution. 

o-Tolyl  Arsine  and  Paraldehyde. 

A similar  experi^ient  v/as  carried  out  to  determine  the  action  of 
paraldehyde  on  o-tolylarsine . To  about  25  grams  of  the  arsine  a few 
drops  of  concentrated  hydrochloric  acid  and  about  35  grams  of  paral- 
dehyde v/ere  added.  The  mixture  became  slightly  warm  but  not  so  warm  I 
as  in  the  previous  experiment.  V/hen  the  reaction  had  ceased,  the 
flask  was  sealed  and  set  aside.  After  a fev;  days  the  mixture  con- 
tained a white  solid  and  v/as  rather  turbid.  The  excess  paraldehyde, 
about  18  gramSjWas  distilled  off  at  180  mm  pressure,  leaving  a clear 
yellow  solution.  An  attempt  was  made  to  distill  this  at  the  sarnie 
pressure,  but  it  decomposed,  turning  red.  At  23  mm.  it  boiled  at 
165°.  On  second  distillation,  about  18  gram.s  of  product,  slightly 


9 


turbid,  v;as  obtained.  In  neither  case  was  all  of  the  product  dis- 
tilled, as  it  charred  slightly  on  getting  to  a lov/  volume.  On  stand- 
ing a few  days  a 'vvliite  solid  settled  out.  fhe  liquid  was  decanted 
from  the  solid  and  on  distillation,  a clear  product,  boiling  at 

165°  21mm.  , v;as  obtained.  The  index  of  refraction  is 
30 

(n)  1.5573  % arsenic 

Calculated  for  C%G6H4AsH2(  CH.-xCHO ) 2 29.25 

.0974  gram  substance  reduced  7.67  c.c.  of 

iodine  solution  ( Ic .c .-.003528  gram  ar- 
senic) 27.78 

.1527  gram,  substance  reduced  12.04  c.c,  of 

iodine  solution  27.82 

fhis  substance  possibly  has  the  structure: 

H 


OH 


similar  to  the  one  suggested  for  the  condensation  product  ofxbenzal 
dehyde  and  o-tolylarsine . ' 

The  paraldehyde  condensation  product  mentioned  above  was  hy- 
drolyzed by  cold,  concentrated  hydrochloric  acid,  giving  a strong 
odor  of  paraldehyde  and  yellov;  and  red  solids.  These  likely  were 
oxidation  products  of  the  o-tolylarsine  which  was  form.ed  by  the  hy- 
drolysis. Boiling  dilute  hydrochloric  hydrolyzes  the  condensation 
product  slightly.  It  is  not  hydrolyzed  v/ith  boiling  dilute  or  cold 
30h  alkali,  but  on  boiling  v/ith  30;^  sodium  hydroxide,  it  is  hydro- 


lyzed. 


0 


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, -.%,%••  V ' ' ' 


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- - ,C 


10 


Summary . 

1.  Condensation  products  were  made  "by  the  action  of  o-tolyl- 
arsine  on  bensaldehyde  and  paraldehyde. 

2.  C?he  condensation  products  are  stable  in  cold  dilute  acid 
and  alkali  but  are  hydrolyzed  by  boiling  dilute  acid.  Both 
are  hydrolyzed  by  cold,  concentrated  hydrochloric  acid.  In 
the  presence  of  cold  alkali,  the  bensaldehyde  product  is  more 
stable  than  the  paraldehyde  condensation  product. 


i'>  ;';  ■■;'i.  ■ ; '‘'i'  ?,  'KV',1|  ''^;‘  ; 


.’  ■ ‘ ■ - •rn  ’ ^^  t ; , ., 


t- 


i 


R' ' «v, . i : ; :™,:i-  ■ ;:AfeU& 


:Rr;' : ■*r., . ’ • ; . .■  . •> : . x:., m.^’ ■ 


‘a.-  <'  . 


' j 


lU  , ‘J 


S'  ‘ ^ • •u  ■ > \V){^  ivlB^ffifrr'iL  ,'■  ^ 

■i^f : , jr:  ;,S'- 

m ^' / : ' vKS ,, .;  ii^,, 

-V  ;■  s.'V': 'I  ' '-x.  X & -S'S 

• > .'•  * ' <’v‘-^--  ' i->  if  ' A '\  •-'  x:'  ■•^•'  ‘*v  '.'"^'•’"i,'  ' ’■/■ 


■ i 


•■  rJ 


''h  ■ 


. -'  . / . X-?  ' . "1  'Tfe!*4| 

' i-«#  , » . ‘>^  »C:  ' . : .'4  ♦ . V'*  ' .• 


'’ll  ► 


*)  s 


;'  '.•X9/A* 


iN-  • , V 

V't  ; 


. < V' 


J ' ‘ 


/ '• 


Mi.;  ■-‘. . ■■ : » ■■. , , . .'^„  M : ., " ■.'*  ,1 


.'.'XiELiiu^^  " v*v;,  /X'iil  .;4X:•v  ^;is,  /jmy 


•jiV-jAl  4 ,'l 


Vil 


11 


±5iblio,3raphy. 

1.  Morgan,  Organic  eompounds  of  Arsenic  and  imtimony,  XVI. 

E.  Palmer  and  Pehn,  Ber.,  1901,  34,  35,93. 

3.  Morgan,  Organic  Compounds  of  Arsenic  and  Antimony,  89;  Pehn, 
Primary  Arsines,  51. 

4.  Pehn,  Am.Ch.  J.,  40,  105,  1908. 

5.  Pehn  and  Wilcox,  Am.  Oh.  J.,  35,35,  1906. 

6.  Pehn,  Primary  Arsines,  51. 

7.  Morgan,  Organic  Compounds  of  Arsenic  and  Antimony,  89; 

Pelm,  Primary  Arsines,  28,  53. 

8.  P.R.P.  254187,  269743. 

9.  P.R.P.  251571. 

10.  P.R.P.  275216. 

11.  P.R.P.  269745,269743. 

12.  Palmer  and  Pehn,  Am.  Ch.  J.,  47,  54,  1912. 

13.  Adams  and  Palmer,  J.  A.  G.  S.,  42,  2575,  1920. 

14.  P.R.P.  250264. 

15.  Robertson,  J.  A.  C.  3.  43,  182,  1921. 


